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CA1295454C - Process for preparing ammine salts of aluminum iodide - Google Patents

Process for preparing ammine salts of aluminum iodide

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Publication number
CA1295454C
CA1295454C CA000575668A CA575668A CA1295454C CA 1295454 C CA1295454 C CA 1295454C CA 000575668 A CA000575668 A CA 000575668A CA 575668 A CA575668 A CA 575668A CA 1295454 C CA1295454 C CA 1295454C
Authority
CA
Canada
Prior art keywords
iodide
aluminum
ammonia
iodine
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA000575668A
Other languages
French (fr)
Inventor
Dieter Peters
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Application granted granted Critical
Publication of CA1295454C publication Critical patent/CA1295454C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/08Hydrazoic acid; Azides; Halogen azides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/78Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Process for preparing ammine salts of aluminum iodide Abstract of the disclosure:

A process for preparing ammine salts of aluminum iodide by reaction of aluminum, an iodine compound and ammonia is reported in which the reactants are reacted without mercury as a catalyst in the liquid ammonia phase at a temperature from 20 to 600°C and a pressure from 8 to 2,000 bar and excess ammonia is evaporated off after the reaction is completed.

The process makes possible the preparation of hexammine-aluminum iodide monoammoniate, hexamminealuminum iodide and pentamminealuminum iodide.

Description

lZ~5;~5~

HOE 8~/H 019 The present invention relates to a process for preparing ammine salts of aluminum iodide, in particular of hexam-minealuminum iodide monoammoniate, of hexamminealuminum iodide and pentamminealuminum iodide, by reaction of aluminum, an iodine compound and ammonia.

Investigat;ons on ammine salts of aluminum iodide have been described by G.W. Watt and J.H. araun in J.Am. Chem.
Soc. Volume 78 (1956), pages 5494 - 5496. It was found that AlI3 x 20NH3 is unstable above -26C. If AlI3 x 20NH3 is heated at reduced pressure, white crystals of AlI3 x 6NH3 are eventually formed at 25C and 10 3 bar. AlI3 x 6NH3 can be converted to All3 x 5NH3 ;n vacuo.

On page 5495 this article reports that aluminum, iodine and ammonia only react with each other if mercury is added i5 as a catalyst.

It is an object of the present invention to report a process for preparing ammine salts of aluminum iodide from aluminum, an iodine compound and ammonia without a mercury catalyst in high purity and in crystalline form and also as a single crystal.

Surprisingly, it was possible to ach;eve th;s object by reacting aluminum, an iodine compound and ammon;a in the d~

12~5~s4 liquid ammonia phase at a temperature from 20 to 600C, in particular from 70 to 200C and at a pressure from 8 to 2000 bar, in particular 20 to 200 bar and evaporat-ing excess ammonia after the reaction is completed.

Hexamminealuminum iodide monoammoniate is obtained from the reaction product by evaporating excess liquid ammonia at a temperature from 10 to 60C, in particular 15 to 30C
at atmospheric pressure.

Hexamminealuminum iodide is obtained from the reaction product by evaporating excess liquid ammonia at a tem-:
perature from 65 to 300C, in particular 80 to 150C, at atmospher;c pressure or aspirating out excess liquid ammonia as a gas at room temperature up to a reduced pressure of 10 3 bar or aspirating out excess liquid ammonia as a gas at a reduced pressure from 0.3 to 0.7 bar and a final temperature of 30 to 50C.

Pentamminealuminum iodide is obtained from the reaction product by evaporating excess ammonia at a temperature from 305 to 380C, in particular 310 to 330C at atmos-pher;c pressure ---In a preferred embodiment, chlorine or an ;norganicchlor;de, preferably aluminum chLoride or ammonium chloride, ;s metered into the reactants as a reaction accelerator in an amount of 0.05 to 10% by weight, ;n part;cular 0.8 to 1.~ by weight, calculated as I used.

`1295~s~

According to the invention, an atomic Al : I ratio of the reactants of 1 : (2 to 3.1) is established.

Elemental ;odine or ammonium iodide can be used as the iodine compound.

S It has been found that in the case of an atomic Al excess with respect to iodine the unconverted aluminum can be separated off from the finished product by screening or the unconverted aluminum and undissolved impurities can be channeled out from the liquid ammonia phase by filtration or decantation.

The ammine salts of aluminum iodide can be incorporated into synthetic resins and synthetic paints as an expand-able flameproofing agent.

The following examples serve to illustrate the invention without limiting it to these examples.

Example 1 27 parts of aluminum shavings and 435 parts of ammonium iodide are initially introduced into an enameled heatable stirred autoclave under inert gas tN2, Ar). After evacuation, 561 parts of ammonia were condensed ;nto the autoclave. After the autoclave had been closed, it was heated to 75C and kept at this temperature for 99 hours.
A pressure of 35 bar was reached. The autoclave was then i295~4 let down to atmospheric pressure at room temperature.
The product gave the follow;ng analysis:

Al0.179 Io,573 N1.289 and therefore corresponded to the formula C Al(NH3)6 ~ I3(NH3) + 0.201 NH4I

The yield was 94Z based on aluminum.

Example 2 27 parts of aluminum shavings and 290 parts of ammonium iodide were initially introduced into the autoclave under inert gas (N2, Ar). After evacuation, 408 parts of ammonia were condensed ;n and the closed autoclave was heated to 400C and kept at 400C and 150 bar for 65 hours.

, The autoclave was let down to atmospheric pressure at 25C

and the product obtained was removed from excess aluminum through a sieve havins a clear mesh width of 0.20 mm.

The conversion based on iodine was 100Z.

The product gave the following analysis:

.
Alo~196 I0.568 N1.326 and therefore corresponded to the following formula .
~ Al(NH3)6 ~ I3(NH3) + 0.037 Al ` 129S~54 Example 3 Example 2 was repeated except that this time 705 parts of ammonia were condensed in. After a reaction time of 65 hours at 400C, the autoclave was cooled to room S temperature and the reaction mixture was removed from the autoclave using a pressure filter. The ammonia in the filtrate was evaporated at room temperature at atmos-pheric pressure. There remained 524 parts of crystals which gave the following analysis:
A~0.187 Io.570 N1.318 The ana~ytical va~ues therefore corresponded to the formula C Al(NH3)6 ] I3tNH3) + 0.048 NH4I

0.44 part of residue remained on the pressure filter, 97%
by weight of which was aluminum.

Example 4 27 parts of aluminum shavings, 435 parts of ammonium iodide and 4 parts of ammonium chloride were initially ~~~ introduced into the autoclave under inert gas tN2, Ar).
After evacuation, 580 parts of ammonia were condensed in.
After the autoclave had been closed, it was heated to 120C and kept at a pressure of 90 bar for 8 hours. It was then let down to atmospheric pressure at 120C.
The product gave the following analysis:

` 1295454 AlO.181 I0.5~1 N1.156 ClO.015 and therefore corresponded to the formula CAl(NH3)6.04] I3 + 0-240 NH4I + 0.075 NH4C

The yield based on aluminum was 92%.

Example 5 Example 1 was repeated except that after 90 hours the autoclave was kept at room temperature for 12 hours. The pressure of the autoclave was then first released at room temperature and ammonia was finally pumped off in an oil pump vacuum up to 10 3 bar. The autoclave was kept at roo0 temperature while the ammonia was being pumped off.
The product gave the folowing analysis:
AlO.179 Io.597 N1.131 and therefore corresponded to the formula ~AltNH3)s,gg} I3 ~ 0.331 NH4I

Example 6 ExampLe 1 was repeated except that after 90 hours the autoclave was cooled to 40C and was let down to atmos-pheric pressure at this temperature. The contents of the autoclave which was kept at 40C were then pumped off up to a pressure of 0.5 bar.
; The crystalline product gave the following analysis:

...... ..

~2~54`~4 A~o 179 Io.594 N1 132 and therefore corresponded to the formula ~Al(NH3)6] I3 + 0.318 NH4I

Example 7 S 27 parts of aluminum shavings, 381 parts of iodine and 4 parts of ammonium chloride were initially introduced into the autoclave under inert gas (Nz, Ar) and after evacuation 540 parts of ammonia were metered in. The autoclave was heated to 320C and kept at this tempera-ture and a pressure of 180 bar for 7 hours. The autoclavewas then let down to atmospheric pressure a temperature of 3Z0C. The product gave the following analysis:
Alo 182 I0.612 No.985 and therefore corresponded to the formula ~Al~NH3)s 05~ I3 + 0.363 NH4I

The yield based on alum;num was 89%.

Example 8 _, Z5 parts of aluminum shav;ngs, 10 parts of aluminum chlor;de and 435 parts of ammonium ;odide were in;t;ally introduced into the autoclave under ;nert gas (Nz, Ar).
After evacuat;on, 475 9 of ammon;a were condensed in.

.... . . .

~Z9~i~

The autoclave was kept at 200C under a pressure of 140 bar for 7 hours. The autoclave was then heated to 310C and let down to atmospheric pressure.
The product gave the following analysis:
AlO.186 Io,595 N1.025 Clo,045 ~and therefore corresponded to the formula CAl(NH3)5 07] I3 + 0.199 NH4I ~ 0.242 NH4C~

. . .

Claims (12)

1. A process for preparing ammine salts of aluminum iodide by reaction of aluminum, an iodine compound and ammonia, which comprises reacting the reactants without mercury as a catalyst in the liquid ammonia phase at a temperature from 20 to 600°C and a pressure from 8 to
2,000 bar and evaporating excess ammonia after the reaction is completed.

2. The process for preparing hexamminealuminum iodide monoammoniate as claimed in claim 1, which comprises evaporating excess liquid ammonia at a temperature from 10 to 60°C at atmospheric pressure.
3. The process for preparing hexamminealuminum iodide as claimed in claim 1, which comprises evaporating excess liquid ammonia at a temperature from 65 to 300°C at atmospheric pressure.
4. The process as claimed in claim 1, wherein excess liquid ammonia is aspirated out as a gas at room temperature up to a reduced pressure of 10 3 bar.
5. The process as claimed in claim 1, wherein excess liquid ammonia is aspirated out as a gas at a reduced pressure from 0.3 to 0.7 bar and a final temperature of 30 to 50°C.
6. The process for preparing pentamminealuminum iodide as claimed in claim 1, which comprises evaporating excess ammonia at a temperature from 305 to 380°C at atmospheric pressure.
7. The process as claimed in claim 1, wherein chlorine or an inorganic chloride is metered into the reactants as a reaction accelerator in an amount of 0.05 to 10%
by weight, based on iodine used.
8. The process as claimed in claim 1, wherein aluminum chloride or ammonium chloride is metered into the reactants as a reaction accelerator in an amount of 0.05 to 10% by weight, based on iodine used.
9. The process as claimed in claim 1, wherein an atomic Al : I ratio of 1 : (2 to 3.1) is established.
10. The process as claimed in claim 1, wherein elemental iodine or ammonium iodide is used as the iodine compound.
11. The process as claimed in claim 1, wherein in the case of an atomic Al excess with respect to iodine the unreacted aluminum is separated off from the finished product by screening.
12. The process as claimed in claim 1, wherein in the case of an atomic Al excess with respect to iodine the unreacted aluminum and undissolved impurities are channeled out from the liquid ammonia phase by fil-tration or decantation.
CA000575668A 1987-09-18 1988-08-25 Process for preparing ammine salts of aluminum iodide Expired - Fee Related CA1295454C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3731456.4 1987-09-18
DE19873731456 DE3731456A1 (en) 1987-09-18 1987-09-18 METHOD FOR THE PRODUCTION OF AMMINE SALTS OF ALUMINUM IODIDE

Publications (1)

Publication Number Publication Date
CA1295454C true CA1295454C (en) 1992-02-11

Family

ID=6336351

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000575668A Expired - Fee Related CA1295454C (en) 1987-09-18 1988-08-25 Process for preparing ammine salts of aluminum iodide

Country Status (6)

Country Link
US (1) US4921688A (en)
EP (1) EP0307669A3 (en)
JP (1) JPH01100013A (en)
KR (1) KR890004980A (en)
CA (1) CA1295454C (en)
DE (1) DE3731456A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1326771C (en) * 2005-10-18 2007-07-18 自贡市金典化工有限公司 The production method of ammonium iodide
CN102134083B (en) * 2011-05-06 2012-08-22 天津市科密欧化学试剂有限公司 Production method of ammonium iodide
KR20250081927A (en) * 2022-10-11 2025-06-05 엔테그리스, 아이엔씨. Compounds and methods for producing aluminates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3694150A (en) * 1970-07-10 1972-09-26 Gustave E Kidde Preparation of monoammonium aluminum tetrafluoride

Also Published As

Publication number Publication date
KR890004980A (en) 1989-05-11
JPH01100013A (en) 1989-04-18
US4921688A (en) 1990-05-01
EP0307669A3 (en) 1990-11-28
EP0307669A2 (en) 1989-03-22
DE3731456A1 (en) 1989-03-30

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